Resin composition and method of forming resist pattern

ABSTRACT

A resin composition includes a resin A, a resin C, and a solvent. The resin A includes a sulfonic-acid-group-containing structural unit in an amount exceeding 5 mol % with respect to total structural units included in the resin A. The resin A has a content of a fluorine atom of 30 mass % or less with respect to a total mass of the resin A. The resin C includes a fluorine atom in a larger content per unit mass than the content of a fluorine atom per unit mass in the resin A. A content of the resin A in the resin composition is lower than a content of the resin C in the resin composition in terms of mass.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part application ofInternational Application No. PCT/JP2017/038925, filed Oct. 27, 2017,which claims priority to Japanese Patent Application No. 2016-214278,filed Nov. 1, 2016. The contents of these applications are incorporatedherein by reference in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a resin composition and a method offorming a resist pattern.

Description of the Related Art

A photolithography technique using a resist material is employed informing a fine circuit in a semiconductor element. According to this,for example, an acid is generated by exposure using radiation via a maskpattern on a coating film of the resist material, and difference insolubility to a development liquid of the resist material is generatedat the exposed part and at the non-exposed part by reaction using theacid as a catalyst, thereby to form a resist pattern on a substrate.

In the above photolithography technique, miniaturization of the circuitis achieved by using a short-wavelength radiation such as an excimerlaser; however, further miniaturization is demanded due to the needs forscale reduction and higher capacity. Accordingly, as a miniaturizationapplication technique, a liquid immersion lithography method is usedthat performs exposure in a state in which a space between the lens ofan exposure apparatus and the resist film is filled with a liquidmedium. According to this liquid immersion lithography method, theaforementioned space is filled with a liquid medium (for example, water)having a larger refractive index (n) in place of a gas such as air ornitrogen, so that the numerical aperture increases, and resolution andfocal depth can be improved.

In forming a resist pattern using the liquid immersion lithographymethod, deficiency such as elution of the resist film or deteriorationin development properties may occur when the liquid medium such as wateris used. In order to solve this problem, a technique of using awater-repellent upper layer film as a protective film on the resist filmis known. However, when in particular a water-based alkali developmentliquid is used as the development liquid, solubility to the developmentliquid decreases even when the upper layer film is made water-repellent,thereby raising a problem of causing residue defects. As means forsolving this problem, a technique of forming a water-repellent upperlayer film using a resin having a strongly acidic group is proposed(see, Japanese Patent No. 5229228).

According to the above technique, the residue defects are suppressed bypromoting the development liquid solubility of a layer formed byintermixing of the resist film and the upper layer film around theinterface between the two layers (this layer may hereafter be referredto as “mixing layer”) by action of the strongly acidic group introducedinto the resin that forms the resist upper layer film.

SUMMARY OF THE INVENTION

According to an aspect of the present invention, a resin compositionincludes a resin A, a resin C, and a solvent. The resin A includes asulfonic-acid-group-containing structural unit in an amount exceeding 5mol % with respect to total structural units included in the resin A.The resin A has a content of a fluorine atom of 30 mass % or less withrespect to a total mass of the resin A. The resin C includes a fluorineatom in a larger content per unit mass than the content of a fluorineatom per unit mass in the resin A. A content of the resin A in the resincomposition is lower than a content of the resin C in the resincomposition in terms of mass.

According to another aspect of the present invention, a method offorming a resist pattern includes applying a photoresist composition ona substrate to form a resist film on the substrate. The resincomposition is applied on the resist film to form a liquid immersionupper layer film on the resist film. Liquid immersion exposure isperformed on the resist film on which the liquid immersion upper layerfilm is formed. The resist film is developed after the liquid immersionexposure.

According to further aspect of the present invention, a method offorming a resist pattern includes applying a photoresist composition ona substrate to form a resist film on the substrate. The resist film isexposed. The exposed resist film is developed with an alkali developmentliquid. The method further includes applying the resin composition on asurface of the resist film after the resist film is formed and beforethe exposed resist film is developed.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In one embodiment, the present invention relates to a resin compositionincluding:

a resin A that contains a sulfonic-acid-group-containing structural unitin an amount exceeding 5 mol % with respect to total structural unitsincluded in the resin A, the resin A having a content of a fluorine atomof 30 mass or less with respect to a total mass of the resin A;

a resin C that contains a fluorine atom in a larger content per unitmass than the content of a fluorine atom per unit mass in the resin A;and

a solvent,

wherein a content of the resin A in the resin composition is lower thana content of the resin C in the resin composition in terms of mass.

In the resin composition, the highly acidic resin A that contains astructural unit having a sulfonic acid group, which is a strongly acidicgroup, in a predetermined amount or more and has a content of a fluorineatom in a predetermined amount or less with respect to a total mass ofthe resin A is liable to be locally distributed around the interfacebetween the resist film and the protective film that is formed on theresist film using the resin composition, so that the residue defects canbe suppressed by promoting the development liquid solubility of themixing layer. At the same time, the highly water-repellent resin C thatcontains a fluorine atom in a larger content per unit mass than thecontent of a fluorine atom per unit mass in the resin A is liable to belocally distributed on the surface of the protective film and exhibitsthe water repellency. In the resin composition, the content of thehighly acidic resin A is set to be lower than the content of the highlywater-repellent resin C, so that the decrease in water repellency of theprotective film on the resist film can be efficiently suppressed, andthe water mark defects on the resist film can be prevented. Further, inthe case of a so-called dry exposure other than the liquid immersionexposure, a mixing layer is formed by the resin composition and acomponent having a low surface free energy that is liable to be locallydistributed on the surface of the resist film, whereby solubility of theresist film to the development liquid can be promoted, and the residuedefects can be suppressed. In particular, when the resist film containsa fluorine-containing polymer, dissolution of the fluorine-containingpolymer having a relatively lower solubility to the alkali developmentliquid can be promoted when the resin composition forms the mixinglayer, so that larger effects can be expected in suppressing the residuedefects. Furthermore, due to water repellency of the protective film,swelling of the pattern by the alkali development liquid can beprevented, thereby improving the pattern shape.

In the resin composition, it is preferable that the content of the resinA in a total mass of resin solid components of the resin composition be0.1 mass % or more and less than 5 mass %. By setting the content of thehighly acidic resin A to be within the aforementioned range, residuedefect preventability and water mark defect preventability can be madecompatible with each other at a high level.

In the resin composition, it is preferable that the content of the resinC in a total mass of resin solid components of the resin composition be10 mass % or more and 98 mass % or less. By setting the content of thehighly water-repellent resin C to be within the aforementioned range,the receding contact angle of water of the upper layer film can beenhanced, and the water mark defect preventability can be furtherimproved.

In the resin composition, it is preferable that the amount of a fluorineatom in the resin A with respect to a total mass of the resin A is 0mass or more and less than 30 mass %, and the amount of a fluorine atomin the resin C with respect to a total mass of the resin C exceeds 40mass %.

The upper layer film composition preferably further includes a resin Bthat contains a sulfonic-acid-group-containing structural unit in anamount exceeding 0 mol % and being 5 mol % or less with respect to totalstructural units included in the resin B and has a content of a fluorineatom per unit mass smaller than the content of a fluorine atom per unitmass in the resin C. The lowly acidic and lowly water-repellent resin Bhas an intermediate property that lies between the property of the resinA and the property of the resin C in view of acidity and waterrepellency. Such a resin B is liable to be locally distributed betweenthe region of the locally distributed resin A around the interfacebetween the upper layer film and the resist film and the region of thelocally distributed resin C around the upper layer film surface, and canform an intermediate region that connects between the two. As a result,the development liquid solubility derived from the highly acidic resin Aand the water repellency derived from the highly water-repellent resin Ccan be exhibited with a better balance.

In the resin composition, it is preferable that the resin A do notcontain a fluorine atom. This can promote the local distribution of theresin A in a neighborhood of the resist film surface and the localdistribution of the resin C in a neighborhood of the upper layer filmsurface, whereby the water repellency of the upper layer film and thedevelopment liquid solubility of the resist film can be furtherenhanced.

In the resin composition, it is preferable that the resin C do notcontain a sulfonic-acid-group-containing structural unit. Thisconfiguration can suppress decrease in the water repellency of the upperlayer film and can prevent the water mark defects more efficiently.

In the resin composition, the resin A may further have acarboxyl-group-containing structural unit. When the resin A has such anacidic group, control of the acidity of the resin A, local distributionof the resin A to the resist film side, removal of the upper layer filmby the development liquid, and the like can be improved.

It is preferable that the receding contact angle of a film formed fromthe resin composition, with respect to water, be 80° or more. When theupper layer film has a receding contact angle within the aforementionedrange, the water mark defects can be more efficiently prevented. Here,in the present specification, the receding contact angle is a contactangle to the resist upper layer film at an end point in the rear, asviewed in the moving direction, of the water droplet. According as thewater repellency or hydrophobicity of the upper layer film surface ishigher, the receding contact angle assumes a higher value.

In the resin composition, it is preferable that thesulfonic-acid-group-containing structural unit in one or both of theresin A and the resin B be represented by the following Formula (1):

(in the Formula (1), Ra is a hydrogen atom or a methyl group, and Rb isa single bond, an oxygen atom, a sulfur atom, or a divalent organicgroup).

The sulfonic-acid-group-containing structural unit represented by theabove Formula (1) can improve the residue defect preventability.

In one embodiment, the present invention relates to a resist upper layerfilm forming resin composition containing the resin compositiondescribed above. Since the resist upper layer film forming resincomposition (which may hereafter be referred to as “upper layer filmcomposition”) contains the resin composition described above, excellentresidue defect preventability and excellent water mark defectpreventability can be exhibited as the upper layer film formed on theresist film. In other words, the aforementioned resin composition can besuitably used as the resist upper layer film forming resin composition.

In another embodiment, the present invention relates to a method offorming a resist pattern, including:

applying a photoresist composition on a substrate to form a resist filmon the substrate;

applying the resin composition on the resist film to form a liquidimmersion upper layer film on the resist film;

performing liquid immersion exposure on the resist film on which theliquid immersion upper layer film is formed; and

developing the resist film after the liquid immersion exposure.

The resist pattern forming method according to the embodiment forms theresist pattern while preventing water mark defects and residue defectswith use of the above resin composition as the resist upper layer filmforming resin composition, so that the targeted resist pattern can beefficiently formed.

In one embodiment, the present invention relates to a developmentmodifier of an alkali development resist, containing the resincomposition described above. Since the development modifier contains theaforementioned resin composition, excellent residue defectpreventability and excellent water mark defect preventability can beexhibited at the time of liquid immersion exposure as the protectivefilm formed on the resist film. On the other hand, at the time of dryexposure, a mixing layer is formed by the resin composition and acomponent having a low surface free energy that is liable to be locallydistributed on the surface of the resist film, whereby solubility of theresist film to the development liquid can be promoted, and the residuedefects can be suppressed. In particular, when the resist film containsa fluorine-containing polymer, dissolution of the fluorine-containingpolymer having a relatively lower solubility to the alkali developmentliquid can be promoted when the resin composition forms the mixinglayer, so that larger effects can be expected in suppressing the residuedefects. Also, due to water repellency of the protective film, swellingof the pattern by the alkali development liquid can be prevented,whereby a desired pattern formability can be imparted. In other words,the aforementioned resin composition can be suitably used as adevelopment modifier.

In the present specification, the “alkali development resist” in a widerange of meaning refers to a resist capable of forming a positive-typeor negative-type pattern due to change in solubility to the alkalidevelopment liquid by action of an acid, and in a narrow range ofmeaning refers to a resist whose solubility to the alkali developmentliquid increases by action of an acid. Also, the “development modifier”refers to an agent that can improve the pattern shape or decrease theresidue defects or water mark defects by being applied to the surface ofthe resist film before the development step.

In still another embodiment, the present invention relates to a methodof forming a resist pattern, including:

applying a photoresist composition on a substrate to form a resist filmon the substrate;

exposing the resist film; and

developing the exposed resist film with an alkali development liquid,

and further including applying the resin composition on a surface of theresist film after the resist film is formed and before the exposedresist film is developed.

The resist pattern forming method according to the embodiment forms theresist pattern while improving the pattern shape and preventing watermark defects and residue defects with use of the above resin compositionas the development modifier, so that the targeted resist pattern can beefficiently formed.

In the resist pattern forming method according to the embodiment, theexposure can be carried out suitably with an extreme ultraviolet ray.The pattern formed by using an extreme ultraviolet ray is extremelyfine, and the influence of residue defects is large. By using theaforementioned resin composition as the development modifier, a mixinglayer is formed by the resin composition and a component having a lowsurface free energy that is liable to be locally distributed on thesurface of the resist film, whereby solubility of the resist film to thedevelopment liquid can be promoted, and the residue defects can besuppressed. In particular, when the resist film contains afluorine-containing polymer, dissolution of the fluorine-containingpolymer having a relatively lower solubility to the alkali developmentliquid can be promoted when the resin composition forms the mixinglayer, so that larger effects can be expected in suppressing the residuedefects. Also, in the step of developing after the exposure, the finepattern is liable to be affected by the swelling of the alkalidevelopment liquid. By forming the protective film with use of thedevelopment modifier, swelling of the pattern by the alkali developmentliquid can be prevented, and an excellent pattern formability can beexhibited.

In the method of forming a resist pattern according to the embodiment,it is preferable that the photoresist composition contain afluorine-atom-containing polymer. Owing to the oil-repellentcharacteristic caused by containing the fluorine atom, thefluorine-atom-containing polymer is liable to be locally distributed inthe resist film surface layer when the resist film is formed. As aresult of this, the components in the resist film can be prevented frommigrating into the protective film of the development modifier.

<Resin Composition>

The resin composition according to the present embodiment contains theresin A, the resin C, and the solvent. Also, in the present embodiment,the content of the resin A in the resin composition is set to be smallerthan the content of the resin C in the resin composition in terms ofmass. The aforementioned resin composition may contain other additivesas long as the effects of the present invention are not degraded. Theaforementioned resin composition can be suitably used as a resist upperlayer film forming resin composition or a development modifier.Hereafter, details will be described by mentioning each embodiment as anexample.

<Resist Upper Layer Film Forming Resin Composition>

A resist upper layer film forming resin composition according to thepresent embodiment contains the resin composition described above.

(Resin A)

The resin A is a resin that contains a sulfonic-acid-group-containingstructural unit in an amount exceeding 5 mol % with respect to totalstructural units included in the resin A and has having a content of afluorine atom of 30 mass % or less with respect to a total mass of theresin A. It is sufficient that the content of thesulfonic-acid-group-containing structural unit in the resin A is withina range exceeding 5 mol % relative to the total structural unitsconstituting the resin A, and is preferably 6 mol % or more, morepreferably 7 mol % or more, and still more preferably 8 mol % or more.On the other hand, the content of the sulfonic-acid-group-containingstructural unit in the resin A is preferably 50 mol % or less, morepreferably 45 mol % or less, and still more preferably 40 mol % or less.By setting the content of the sulfonic-acid-group-containing structuralunit in the resin A to be within the aforementioned range, decrease inthe water repellency can be suppressed while improving the developmentproperties of the resist film.

(Sulfonic-Acid-Group-Containing Structural Unit)

The sulfonic-acid-group-containing structural unit is preferably astructural unit represented by the following Formula (1) (which mayhereafter be also referred to as “structural unit (1)”, and the sameapplies to other structural units as well).

(in the Formula (1), Ra is a hydrogen atom or a methyl group, and Rb isa single bond, an oxygen atom, a sulfur atom, or a divalent organicgroup).

A hydrogen atom is preferable as Ra in view of copolymerizability andacidity.

The divalent organic group represented by Rb is preferably a divalentchain hydrocarbon group having one to six carbon atoms, a divalentalicyclic hydrocarbon group having four to twelve carbon atoms, adivalent aromatic hydrocarbon group having six to twelve carbon atoms,or —C(═O)—X′—R′— group. Here, X′ is an oxygen atom, a sulfur atom, or anNH group. R′ is a single bond, a divalent chain hydrocarbon group havingone to six carbon atoms, a divalent alicyclic hydrocarbon group havingfour to twelve carbon atoms, or a divalent aromatic hydrocarbon grouphaving six to twelve carbon atoms.

Examples of the divalent chain hydrocarbon group having one to sixcarbon atoms represented by the above Rb and R′ include alkanediylgroups such as methanediyl group, ethanediyl group, and propanediylgroup; alkenediyl groups such as ethenediyl group, propenediyl group,and butenediyl group; and alkynediyl groups such as ethynediyl group,propynediyl group, and butynediyl group.

Examples of the divalent alicyclic hydrocarbon group having four totwelve carbon atoms represented by the above Rb and R′ includemonocyclic cycloalkanediyl groups such as cyclopentanediyl group,cyclohexanediyl group, and cyclooctanediyl group; monocycliccycloalkenediyl groups such as cyclopentenediyl group, cyclohexenediylgroup, and cyclooctenediyl group; polycyclic cycloalkanediyl groups suchas norbornanediyl group and adamantanediyl group; and polycycliccycloalkenediyl groups such as norbornenediyl group and tricyclodecenylgroup.

Examples of the divalent aromatic hydrocarbon group having six to twelvecarbon atoms represented by the above Rb and R′ include phenylene group,tolylene group, and naphthylene group.

The above Rb is preferably a single bond, a divalent chain hydrocarbongroup having one to six carbon atoms, a divalent aromatic hydrocarbongroup having six to twelve carbon atoms, or —C(═O)—NH—R′— group in whichR′ is a divalent chain hydrocarbon group having one to six carbon atoms,more preferably a single bond, methanediyl group, phenylene group, or—C(═O)—NH—CH(CH₃)—CH₂—, still more preferably a single bond or—C(═O)—NH—CH(CH₃)—CH₂—.

Examples of the above structural unit (1) include structural unitsrepresented by the following Formulas (1-1) to (1-4).

In the above Formulas (1-1) to (1-4), Ra has the same meaning as in theabove Formula (1). Among these, the structural unit (1-1) is preferable.

The resin A may contain one kind or two or more kinds of the structuralunits (1) in combination.

(Carboxyl-Group-Containing Structural Unit)

The resin A preferably contains a carboxyl-group-containing structuralunit in addition to the sulfonic-acid-group-containing structural unitdescribed above. When the resin A contains such an acidic group, controlof the acidity of the resin A, local distribution of the resin A to theresist film side, removal of the upper layer film by the developmentliquid, and the like can be improved.

The carboxyl-group-containing structural unit is preferably a structuralunit represented by the following Formula (2) (which may hereafter bealso referred to as “structural unit (2)”).

In the above Formula (2), R^(E) is a hydrogen atom, a fluorine atom, amethyl group, or a trifluoromethyl group. Here, k is an integer of 0 to3. When k is 1 to 3, L¹ is a (k+1)-valent linking group. When k is 0, L¹is a hydrogen atom.

The above R^(E) is preferably a hydrogen atom or a methyl group, morepreferably a methyl group, in view of copolymerizability of the monomersgiving the structural unit (2) and the like.

Examples of the (k+1)-valent linking group represented by the above L¹include an alkanediyl group, a cycloalkanediyl group, an alkenediylgroup, and an arenediyl group as the divalent linking groups (when k andm are 1). Here, a part or whole of the hydrogen atoms that these groupshave may be substituted with halogen atoms such as a fluorine atom or achlorine atom, a cyano group, or the like.

Examples of the above alkanediyl group include methanediyl group,ethanediyl group, propanediyl group, butanediyl group, hexanediyl group,and octanediyl group. The above alkanediyl group is preferably analkanediyl group having one to eight carbon atoms.

Examples of the above cycloalkanediyl group include monocycliccycloalkanediyl groups such as cyclopentanediyl group andcyclohexanediyl group; and polycyclic cycloalkanediyl groups such asnorbornanediyl group and adamantanediyl group. The above cycloalkanediylgroup is preferably a cycloalkanediyl group having five to twelve carbonatoms.

Examples of the above alkenediyl group include ethenediyl group,propenediyl group, and butenediyl group. The above alkenediyl group ispreferably an alkenediyl group having two to six carbon atoms.

Examples of the above arenediyl group include phenylene group, tolylenegroup, and naphthylene group. The above arenediyl group is preferably anarenediyl group having six to fifteen carbon atoms.

Among these, L¹ is preferably an alkanediyl group or a cycloalkanediylgroup, and more preferably is an alkanediyl group having one to fourcarbon atoms or a cycloalkanediyl group having six to eleven carbonatoms. When L¹ is a cycloalkanediyl group, it is preferable in view ofenhancing the water repellency of the resist upper layer film formedfrom the resist upper layer film forming resin composition.

The above k is preferably an integer of 0 to 2, more preferably 0 or 1,and still more preferably 0.

Examples of the above structural unit (2) include structural unitsrepresented by the following Formulas (2-1) to (2-3).

In the above Formulas (2-1) to (2-3), R^(E) has the same meaning as inthe above Formula (2). In the above Formulas (2-1) and (2-2), R^(c1) andR^(c2) are each independently a divalent chain hydrocarbon group havingone to six carbon atoms, a divalent alicyclic hydrocarbon group havingfour to twelve carbon atoms, or a divalent aromatic hydrocarbon grouphaving six to twelve carbon atoms.

Examples of the divalent chain hydrocarbon group having one to sixcarbon atoms represented by the above R^(c1) and R^(c2) includealkanediyl groups such as methanediyl group, ethanediyl group,propanediyl group, butanediyl group, hexanediyl group, and octanediylgroup; alkenediyl groups such as ethenediyl group, propenediyl group,and butenediyl group; and alkynediyl groups such as ethynediyl group.

Examples of the divalent alicyclic hydrocarbon group having four totwelve carbon atoms represented by the above R^(c1) and R^(c2) includemonocyclic cycloalkanediyl groups such as cyclopentanediyl group andcyclohexanediyl group; polycyclic cycloalkanediyl groups such asnorbornanediyl group and adamantanediyl group; monocycliccycloalkenediyl groups such as cyclopentenediyl group; and polycycliccycloalkenediyl groups such as norbornenediyl group.

Among these, a saturated chain hydrocarbon group and a monocyclichydrocarbon group are preferable, and 1,2-ethanediyl group and1,2-cyclohexanediyl group are more preferable.

Examples of the divalent aromatic hydrocarbon group having six to twelvecarbon atoms represented by the above R^(c1) and R^(c2) include groupssimilar to those exemplified as Rb in the above Formula (1).

Examples of the structural units (2-1) and (2-2) include structuralunits represented by the following Formulas (2-1-1) to (2-1-5).

In the above Formulas (2-1-1) to (2-1-5), R^(E) has the same meaning asin the above Formula (2).

Among the structural units (2-1) to (2-3), the structural unitrepresented by the above Formula (2-1) and the structural unitrepresented by the Formula (2-3) are preferable. Also, among thestructural unit represented by the above Formula (2-1), the structuralunit represented by the Formula (2-1-1) is preferable.

The resin A may contain one kind or two or more kinds of the structuralunits (2) in combination.

The content (the sum in the case in which two or more kinds arecontained) of the structural unit (2) in the resin A is preferably 5 mol% to 95 mol %, more preferably 10 mol % to 92 mol %, and still morepreferably 20 mol % to 90 mol %, relative to the total structural unitsconstituting the resin A. By setting the content of the structural unit(2) in the resin A to be within the aforementioned range, control of theacidity of the resin A, local distribution of the resin A to the resistfilm side, removal of the upper layer film by the development liquid,and the like can be improved.

(Fluorinated-Hydrocarbon-Group-Containing Structural Unit (I))

The resin A may contain a fluorinated-hydrocarbon-group-containingstructural unit (I) besides the structural units (1) and (2). Byintroducing the fluorinated-hydrocarbon-group-containing structural unit(I) while sufficiently ensuring the acidity of the resin A, the waterrepellency of the upper layer film formed with use of the upper layerfilm composition can be suitably controlled.

The fluorinated-hydrocarbon-group-containing structural unit (I) ispreferably a structural unit having at least one kind selected from thegroup consisting of the group represented by the following Formula (3)(fluorinated sulfonamide group) and the group represented by thefollowing Formula (4) (α-trifluoromethyl alcohol group) (hereafter, thestructural unit containing the group represented by the followingFormula (3) is also referred to as “structural unit (3)”, and thestructural unit containing the group represented by the followingFormula (4) is also referred to as “structural unit (4)”.

In the above Formula (3), R¹⁰ is a monovalent fluorinated hydrocarbongroup having one to twenty carbon atoms. In the above Formula (4), R₁₁is a monovalent fluorinated hydrocarbon group having one to twentycarbon atoms, and R¹² is a hydrogen atom or a monovalent organic grouphaving one to twenty carbon atoms.

Examples of the monovalent fluorinated hydrocarbon group having one totwenty carbon atoms represented by the above R¹⁰ and R¹¹ include groupsin which a part or whole of the hydrogen atoms that the saturated orunsaturated chain hydrocarbon groups, monocyclic or polycyclic alicyclichydrocarbon groups, aryl groups, or aralkyl groups have are substitutedwith fluorine atoms. Examples of the polycyclic structure includecross-linked polycyclic structures such as a norbornane structure, anadamantane structure, and a tricyclodecane structure in addition to thecondensed-ring structure.

Examples of the monovalent organic group represented by the above R¹²include a monovalent hydrocarbon group having one to twenty carbonatoms, a monovalent heteroatom-containing group containing a grouphaving a heteroatom between carbon-carbon of this hydrocarbon group, anda monovalent group in which a part or whole of the hydrogen atoms thatthe above hydrocarbon group or the heteroatom-containing group has aresubstituted with a substituent.

Examples of the above monovalent hydrocarbon group include chainhydrocarbon groups such as alkyl groups such as methyl group, ethylgroup, propyl group, and butyl group; alkenyl groups such as ethenylgroup, propenyl group, and butenyl group; and alkynyl groups such asethynyl group, propynyl group, and butynyl group; alicyclic hydrocarbongroups such as cycloalkyl groups such as cyclopentyl group, cyclohexylgroup, norbornyl group, and adamantyl group; and cycloalkenyl groupssuch as cyclopentenyl group and norbornenyl group; and aromatichydrocarbon groups such as aryl groups such as phenyl group, tolylgroup, xylyl group, naphthyl group, and anthryl group; and aralkylgroups such as benzyl group, phenethyl group, and naphthylmethyl group.

The heteroatom in the aforementioned group having a heteroatom is notparticularly limited as long as the heteroatom is an atom other than acarbon atom or a hydrogen atom, and examples thereof include an oxygenatom, a nitrogen atom, a silicon atom, a phosphorus atom, and a sulfuratom. Examples of the above group having a heteroatom include —CO—,—COO—, —O—, —NR″—, —CS—, —S—, —SO—, —SO₂—, and groups obtained bycombining these.

Examples of the above substituent include halogen atoms such as afluorine atom, a chlorine atom, a bromine atom, and an iodine atom,hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group,alkoxycarbonyl group, acyl group, and acyloxy group.

R¹² is preferably a group having a hydrogen atom, a monovalenthydrocarbon group, a monovalent fluorinated hydrocarbon group, or ahydroxyl group, more preferably a group having a hydrogen atom, an alkylgroup, a fluorinated alkyl group, a hydroxyl group, or a fluorine atom,still more preferably a group containing a hydrogen atom, an alkyl grouphaving one to six carbon atoms, a fluorinated alkyl group having one tosix carbon atoms, or a di (trifluoromethyl) hydroxymethyl group havingone to six carbon atoms, and particularly preferably a hydrogen atom,methyl group, ethyl group, 1,1,1-trifluoromethyl group,2,2,2-trifluoroethyl group, or2-hydroxy-2-trifluoromethyl-1,1,1-trifluoro-4-butyl group.

Examples of the above structural unit (3) include structural unitsrepresented by the following Formula (3-1) (which may hereafter be alsoreferred to as “structural unit (3-1)”)

In the above Formula (3-1), R^(C) is a hydrogen atom, a methyl group, afluorine atom, or a trifluoromethyl group. R^(n1) is a divalent linkinggroup. R^(n2) is a fluorinated alkyl group having one to twenty carbonatoms.

The above R^(C) is preferably a hydrogen atom or a methyl group, morepreferably a methyl group, in view of copolymerizability of the monomersgiving the structural unit (3-1) and the like.

Examples of the above divalent linking group represented by R^(n1)include a divalent chain hydrocarbon group having one to six carbonatoms, a divalent alicyclic hydrocarbon group having four to twelvecarbon atoms, and a group containing —O—, —CO—, or —COO— betweencarbon-carbon of these groups.

Examples of the above divalent chain hydrocarbon group having one to sixcarbon atoms include a group in which two of the hydrogen atomscontained in saturated or unsaturated chain hydrocarbon groups have beenremoved.

Examples of the above divalent alicyclic hydrocarbon group having fourto twelve carbon atoms include a group in which two of the hydrogenatoms contained in monocyclic or polycyclic alicyclic hydrocarbon groupshave been removed.

Among these, R^(n1) is preferably a divalent chain hydrocarbon grouphaving one to three carbon atoms, more preferably an alkanediyl grouphaving one to three carbon atoms, and more preferably 1,2-ethanediylgroup.

Examples of the above fluorinated alkyl group having one to twentycarbon atoms represented by R^(n2) include fluoromethyl group,difluoromethyl group, trifluoromethyl group, trifluoroethyl group,pentafluoromethyl group, heptafluoropropyl group, and nonafluorobutylgroup. Among these, trifluoromethyl group is preferable.

Examples of the above structural unit (4) include structural unitrepresented by the following Formula (4-1) (which may hereafter be alsoreferred to as “structural unit (4-1)”).

In the above Formula (4-1), R^(D) is a hydrogen atom, a fluorine atom, amethyl group, or a trifluoromethyl group. R^(t1) is a divalent linkinggroup.

The above R^(D) is preferably a hydrogen atom or a methyl group, morepreferably a methyl group, in view of copolymerizability of the monomersgiving the structural unit (4-1) and the like.

The above divalent linking group represented by R^(t1) include groupssimilar to those exemplified as R^(n1) in the above Formula (3-1). Amongthese, R^(t1) is preferably a divalent chain hydrocarbon group havingone to three carbon atoms or a divalent alicyclic hydrocarbon grouphaving four to twelve carbon atoms, more preferably a divalent groupcontaining a propanediyl group or a cyclohexane skeleton, a divalentgroup containing a norbornane skeleton, a divalent group containing atetracyclododecane skeleton, or a divalent group containing anadamantane skeleton, more preferably 1,2-propanediyl group or1-cyclohexyl-1,2-ethanediyl group.

Examples of the structural unit (4-1) include structural unitsrepresented by the following Formulas (4-1-1) to (4-1-8).

In the above Formulas (4-1-1) to (4-1-8), R^(D) has the same meaning asin the above Formula (4-1).

Among these, the structural unit represented by the above Formula(4-1-4) and the structural unit represented by the Formula (4-1-8) arepreferable.

The resin A may contain one kind or two or more kinds of thefluorinated-hydrocarbon-group-containing structural units (I) incombination.

The content of the fluorinated-hydrocarbon-group-containing structuralunit (I) in the resin A is preferably 0 mol % to 50 mol %, morepreferably 5 mol % to 40 mol %, still more preferably 10 mol % to 30 mol%, and particularly preferably 15 mol % to 25 mol %, relative to thetotal structural units constituting the resin A. By setting the contentof the fluorinated-hydrocarbon-group-containing structural unit (I) inthe resin A to be within the aforementioned range, the balance betweenthe water repellency of the upper layer film formed from the upper layerfilm composition and the removal of the upper layer film can be furtherimproved.

(Other Structural Units)

The resin A may have other structural units besides the above structuralunits (1) to (4). Examples of the above other structural units includestructural units derived from alkyl (meth)acrylates such as methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate, and lauryl (meth)acrylate, in view of improving thewater repellency. Also, the examples include structural units having anacid-dissociative group in view of controlling the molecular weight,glass transition point, solubility to the solvent, and the like of theresin A. In the present specification, the “acid-dissociative group”refers to a group that substitutes for a hydrogen atom owned by acarboxyl group has and that is dissociated by action of an acid.

It is possible to adopt a configuration such that the resin A does notcontain the aforementioned other structural units. Also, when the resinA contains the aforementioned other structural units, the content of theaforementioned other structural units in the resin A is preferably 10mol or more, more preferably 20 mol % or more, and still more preferably30 mol % or more, relative to the total structural units constitutingthe resin A. On the other hand, the aforementioned content is preferably90 mol % or less, more preferably 80 mol % or less, and still morepreferably 70 mol % or less.

(Content of Fluorine Atom in Resin A)

It is possible to adopt a configuration such that the resin A does notcontain a fluorine atom. This can promote the local distribution of theresin A in a neighborhood of the resist film surface and the localdistribution of the resin C in a neighborhood of the upper layer filmsurface, and can further enhance the water repellency of the upper layerfilm and the development liquid solubility of the resist film.Alternatively, the resin A may contain a fluorine atom. When the resin Acontains a fluorine atom, the amount of the fluorine atom contained inthe resin A with respect to a total mass of the resin A is preferably 30mass % or less, more preferably 1 mass % or more and 25 mass % or less,and still more preferably 5 mass % or more and 20 mass or less. Thewater repellency of the resin A can be controlled by the content of thefluorine atoms in the resin A.

In the upper layer film composition, the content of the resin A issmaller than the content of the resin C (which will be described later).In the upper layer film composition, it is preferable that the contentof the resin A in a total mass of resin solid components of the upperlayer film composition be 0.1 mass % or more and less than 5 mass %,more preferably 0.3 mass % or more and less than 4.8 mass %, and stillmore preferably 0.5 mass % or more and less than 4.5 mass %. By settingthe content of the highly acidic resin A to be within the aforementionedrange, residue defect preventability and water mark defectpreventability can be made compatible with each other at a high level.

(Resin C)

The resin C is a resin containing a fluorine atom in a larger contentper unit mass than the content of a fluorine atom per unit mass in theresin A. It is sufficient that the content of the fluorine atomsatisfies this relationship; however, the amount of the fluorine atomcontained in the resin C with respect to a total mass of the resin Cpreferably exceeds 40 mass %, and more preferably is 42 mass % or more,still more preferably 44 mass % or more, and particularly preferably 45mass % or more. The amount of the fluorine atom contained in the resin Cwith respect to a total mass of the resin C is preferably 60 mass % orless, more preferably 55 mass % or less, and still more preferably 53mass % or less, in view of the solubility of the upper layer film formedby the upper layer film composition to the development liquid, thefacility of synthesizing the resin C, and the like.

The resin C preferably contains the aforementionedfluorinated-hydrocarbon-group-containing structural unit (I).Compatibility between the water repellency of the upper layer filmformed by using the upper layer film composition and the developmentliquid solubility of the resist film can be further enhanced.

The content of the fluorinated-hydrocarbon-group-containing structuralunit (I) in the resin C is preferably 10 mol % to 100 mol %, morepreferably 20 mol % to 90 mol %, still more preferably 30 mol % to 70mol %, and particularly preferably 35 mol % to 60 mol %, relative to thetotal structural units constituting the resin C. By setting the contentof the fluorinated-hydrocarbon-group-containing structural unit (I) inthe resin C to be within the aforementioned range, the balance betweenthe water repellency of the upper layer film formed from the upper layerfilm composition and the removal of the upper layer film can be furtherimproved.

(Fluorinated-Hydrocarbon-Group-Containing Structural Unit (II))

The resin C may contain a fluorinated-hydrocarbon-group-containingstructural unit (II) that is different from the aforementionedfluorinated-hydrocarbon-group-containing structural unit (I). This canimprove the water repellency of the upper layer film formed by using theupper layer film composition.

Although not particularly limited, the fluorinated hydrocarbon group maybe, for example, a fluorinated alkyl group or a fluorinated cycloalkylgroup.

The fluorinated alkyl group may be, for example, a group in which a partor whole of the hydrogen atoms that the straight-chain or branched alkylgroups have are substituted with a fluorine atom.

The fluorinated cycloalkyl group may be, for example, a group in which apart or whole of the hydrogen atoms that the monocyclic or polycycliccycloalkyl groups have are substituted with a fluorine atom.

The fluorinated-hydrocarbon-group-containing structural unit (II) ispreferably a structural unit represented by the following Formula (5).

In the above Formula (5), R^(B) is a hydrogen atom, a methyl group, afluorine atom, or a trifluoromethyl group. Rf is a fluorinated alkylgroup or a fluorinated cycloalkyl group.

The above R^(B) is preferably a hydrogen atom or a methyl group, morepreferably a methyl group, in view of the copolymerizability of themonomers giving the structural unit (5) and the like.

The above Rf is preferably a fluorinated alkyl group, more preferably afluorinated alkyl group having one to four carbon atoms, still morepreferably a fluorinated alkyl group having two or three carbon atoms,and particularly preferably 2,2,2-trifluoroethyl group or1,1,1,3,3,3-hexafluoro-2-propyl group.

Examples of the structural unit (5) include structural units representedby the following Formulas (5-1) to (5-6).

In the above Formulas (5-1) to (5-6), R^(B) has the same meaning as inthe above Formula (5).

Among these, the structural unit represented by the above Formula (5-1)and the structural unit represented by the Formula (5-3) are preferable.

It is sufficient that the content of thefluorinated-hydrocarbon-group-containing structural unit (II) in theresin C is selected so that the aforementioned amount of the fluorineatom contained per unit mass may be obtained. The content of thefluorinated-hydrocarbon-group-containing structural unit (II) in theresin C is preferably 20 mol % to 80 mol %, more preferably 25 mol % to75 mol %, and still more preferably 30 mol % to 70 mol %, relative tothe total structural units constituting the resin C. By setting thecontent of the fluorinated-hydrocarbon-group-containing structural unit(II) in the resin C to be within the aforementioned range, sufficientwater repellency can be imparted to the resist upper layer film formedfrom the upper layer film composition.

(Other Structural Units)

The resin C may contain the structural units (1) to (2) and otherstructural units that can be used in the resin A besides theaforementioned fluorinated-hydrocarbon-group-containing structural units(I) and (II) unless the water repellency of the resin C is degraded.However, it is preferable that the resin C do not contain asulfonic-acid-group-containing structural unit. By not introducing thesulfonic acid group which is a strong acid, decrease in the waterrepellency of the upper layer film can be suppressed, and the water markdefects can be more efficiently prevented.

In the upper layer film composition, it is preferable that the contentof the resin C in a total mass of resin solid components of the upperlayer film composition be 10 to 98 mass %, more preferably 15 to 95 mass%, and still more preferably 20 to 90 mass %. By setting the content ofthe highly water-repellent resin C to be within the aforementionedrange, the receding contact angle of water of the upper layer film canbe enhanced, and the water mark defect preventability can be furtherimproved.

(Resin B)

The resist upper layer film forming composition according to the presentembodiment preferably further includes a resin B that contains asulfonic-acid-group-containing structural unit in an amount exceeding 0mol % and being 5 mol % or less with respect to total structural unitsincluded in the resin B and has a content of a fluorine atom per unitmass smaller than the content of a fluorine atom per unit mass in theresin C. By incorporating the lowly acidic and lowly water-repellentresin B, the development liquid solubility derived from the highlyacidic resin A and the water repellency derived from the highlywater-repellent resin C can be exhibited with a better balance.

(Sulfonic-Acid-Group-Containing Structural Unit)

The structural unit (1) contained in the resin A can be suitably used asthe sulfonic-acid-group-containing structural unit contained in theresin B. It is sufficient that the content of thesulfonic-acid-group-containing structural unit in the resin B is withina range exceeding 0 mol % and being 5 mol % or less relative to thetotal structural units constituting the resin B. The content ispreferably 4.8 mol % or less, more preferably 4.5 mol % or less, andstill more preferably 4.2 mol % or less. On the other hand, the contentis preferably 0.5 mol % or more, more preferably 1 mol % or more, andstill more preferably 1.5 mol % or more.

(Other Structural Units)

The resin B may contain the structural units (2) to (4) and otherstructural units that can be used in the resin A besides theaforementioned sulfonic-acid-group-containing structural unit.

When the resin B contains the structural unit (2), the content of thestructural unit (2) is preferably 20 mol % to 98 mol %, more preferably30 mol % to 96 mol %, and still more preferably 40 mol % to 90 mol %,relative to the total structural units constituting the resin B.

When the resin B contains the fluorinated-hydrocarbon-group-containingstructural unit (I), the content of thefluorinated-hydrocarbon-group-containing structural unit (I) (structuralunits (3) and (4)) is selected within a range such that the amount ofthe fluorine atom contained per unit mass is smaller than in the resinC. The content of the fluorinated-hydrocarbon-group-containingstructural unit (I) may occupy the whole of the rest parts excluding thesulfonic-acid-group-containing units, and is preferably 50 mol % to 99mol %, more preferably 60 mol % to 98 mol %.

When the upper layer film composition contains the resin B, the contentof the resin B in the total mass of resin solid components of the upperlayer film composition is preferably 10 to 90 mass %, more preferably 10to 85 mass %, and still more preferably 15 to 80 mass %. By setting thecontent of the resin B to be within the aforementioned range, each ofthe functions of the resin A and the resin B can be sufficientlyexhibited, and the water repellency of the upper layer film and thesolubility to the development liquid can be optimized.

(Method of Synthesizing Each Resin)

The aforementioned resin A can be synthesized, for example, bysubjecting a predetermined monomer to polymerization such as radicalpolymerization in a polymerization solvent in the presence of a suitablyselected polymerization initiator or chain-transfer agent.

Examples of the aforementioned polymerization solvent includealcohol-based solvents, ether-based solvents, ketone-based solvents,ester-based solvents, and hydrocarbon-based solvents.

Examples of the alcohol-based solvents include aliphatic monoalcoholshaving one to eighteen carbon atoms such as 4-methyl-2-pentanol andn-hexanol; alicyclic monoalcohols having three to eighteen carbon atomssuch as cyclohexanol; polyhydric alcohols having two to eighteen carbonatoms such as 1,2-propylene glycol; and polyhydric alcohol partialethers having three to nineteen carbon atoms such as propylene glycolmonomethyl ether.

Examples of the ether-based solvents include dialkyl ethers having twoto fourteen carbon atoms such as diethyl ether and dipropyl ether;cyclic ethers such as tetrahydrofuran and tetrahydropyran; andaromatic-ring-containing ethers such as diphenyl ether and anisole.

Examples of the ketone-based solvents include chain ketones having threeto twelve carbon atoms such as acetone, methyl ethyl ketone, andmethyl-n-butyl ketone; cyclic ketones having five to eight carbon atomssuch as cyclopentanone and cyclohexanone; 2,4-pentanedione,acetonylacetone, and acetophenone.

Examples of the ester-based solvents include monocarboxylic acid esterssuch as n-butyl acetate and ethyl lactate; polyhydric alcoholcarboxylates such as propylene glycol acetate; polyhydric alcoholpartial ether carboxylates such as propylene glycol monomethyl etheracetate; polycarboxylic acid diesters such as diethyl oxalate; andcarbonates such as dimethyl carbonate and diethyl carbonate.

Examples of the hydrocarbon-based solvents include aliphatichydrocarbons having five to twelve carbon atoms such as n-pentane andn-hexane; and aromatic hydrocarbons having six to sixteen carbon atomssuch as toluene and xylene.

Among these, alcohol-based solvents, ether-based solvents, ketone-basedsolvents, or ester-based solvents are preferable, and aliphaticmonoalcohols, cyclic ethers, and chain or cyclic ketones are morepreferable. One kind or two or more kinds of the aforementionedpolymerization solvents can be used.

The weight-average molecular weight (Mw), as converted in terms ofpolystyrene, of the resin A by gel permeation chromatography (GPC) ispreferably 2,000 to 50,000, more preferably 3,000 to 30,000, still morepreferably 5,000 to 20,000, and particularly preferably 6,000 to 13,000.By setting the Mw of the resin A to be above or equal to theaforementioned lower limit, moisture resistance and mechanicalproperties as the upper layer film can be improved. By setting the Mw ofthe resin A to be below or equal to the aforementioned upper limit, thesolubility of the resin A to the solvent can be enhanced.

The ratio (Mw/Mn) of the Mw of the resin A to the number-averagemolecular weight (Mn), as converted in terms of polystyrene, of theresin A by GPC is preferably 1 to 5, more preferably 1 to 3, and stillmore preferably 1 to 2.5.

The amount of impurities, such as halogen ions and metals, contained inthe upper layer film composition is preferably as little as possible. Byreducing the amount of the impurities, the application property as theupper layer film and the uniform solubility to the alkali developmentliquid can be improved. As a method for purifying the resin A in orderto reduce the amount of the impurities, for example, washing,extraction, adsorption, filtration, centrifugal separation, and the likemay be carried out either singly or in combination of these.

(Solvent)

The resist upper layer film forming resin composition according to thepresent embodiment contains a solvent. Any solvent can be used as longas the solvent can dissolve or disperse each resin component and theadditives that are added in accordance with the needs. Among these, itis possible to suitably use a solvent that invites little decrease inthe lithography performance caused by generation of excessiveintermixing with the resist film upon applying the upper layer filmcomposition onto the resist film.

Examples of the solvent include alcohol-based solvents, ether-basedsolvents, hydrocarbon-based solvents, ketone-based solvents, ester-basedsolvents, and water.

Examples of the alcohol-based solvents include monohydric alcohols suchas butanol and pentanol; polyhydric alcohols such as ethylene glycol andpropylene glycol; and partial alkyl ethers of polyhydric alcohol such asethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

Examples of the ether-based solvents include alkyl ethers of polyhydricalcohol such as ethylene glycol dimethyl ether, ethylene glycol methylethyl ether, ethylene glycol diethyl ether, and diethylene glycoldimethyl ether; aliphatic ethers such as diethyl ether, dipropyl ether,dibutyl ether, butyl methyl ether, butyl ethyl ether, diisoamyl ether,hexyl methyl ether, octyl methyl ether, cyclopentyl methyl ether, anddicyclopentyl ether; aliphatic-aromatic ethers such as anisole andphenyl ethyl ether; and cyclic ethers such as tetrahydrofuran,tetrahydropyran, and dioxane.

Examples of the hydrocarbon-based solvents include lower hydrocarbonssuch as hexane, cyclohexane, and heptane; and higher hydrocarbons suchas decane, dodecene, and undecane.

Examples of the ketone-based solvents include dialkyl ketones such asacetone and methyl ethyl ketone; and cyclic ketones such ascyclopentanone and cyclohexanone.

Examples of the ester-based solvents include alkyl ether acetates ofpolyhydric alcohol such as ethylene glycol monomethyl ether acetate,ethylene glycol monoethyl ether acetate, diethylene glycol monomethylether acetate, and diethylene glycol monoethyl ether acetate; andaliphatic acid esters such as ethyl acetate and butyl acetate.

Among these, alcohol-based solvents, ether-based solvents, andester-based solvents are preferable. As the alcohol-based solvents,monohydric alcohols and partial alkyl ethers of polyhydric alcohol arepreferable. As the ether-based solvents, aliphatic ethers, cyclicethers, and alkyl ethers of polyhydric alcohol are preferable. As theester-based solvents, alkyl ether acetates of polyhydric alcohol arepreferable. Among these, monohydric alcohols having four to ten carbonatoms and aliphatic ethers having an alkyl chain and having four to tencarbon atoms are more preferable, and 4-methyl-2-pentanol and diisoamylether are particularly preferable. When the solvent contains anether-based solvent, the resist upper layer film forming resincomposition can have a reduced viscosity, and the application amountthereof can be effectively reduced. As a result of this, the costs canbe advantageously reduced.

(Additives)

In addition to each resin component and the solvent, the resist upperlayer film forming resin composition may contain additives. Examples ofthe additives include surfactants.

Examples of the surfactants include commercially availablefluorine-based surfactants such as BM-1000 and BM-1100 (these two aremanufactured by BM Chemie), and MEGAFAC F142D, MEGAFAC F172, MEGAFACF173, and MEGAFAC F183 (these four are manufactured by DIC Corporation).The content of the aforementioned surfactants is preferably 5 parts bymass or less relative to 100 parts by mass of the resin components.

(Receding Contact Angle of Resist Upper Layer Film)

The receding contact angle of an upper layer film formed from the upperlayer film composition, with respect to water, is desirably 75° or morein view of the throughput at the time of liquid immersion exposure andthe yield, preferably 80° or more, more preferably 81° or more, andstill more preferably 82° or more. When the upper layer film has areceding contact angle within the aforementioned range, the waterrepellency of the upper layer film is further enhanced, and the watermark defects can be more efficiently prevented.

<Method of Preparing Resist Upper Layer Film Forming Composition>

The resist upper layer film forming resin composition can be prepared,for example, by mixing and dissolving each resin component and optionaladditives added in accordance with the needs with a solvent. The solidcomponent concentration of the resist upper layer film forming resincomposition is typically 0.5 mass % to 30 mass %, preferably 1 mass % to20 mass %.

<Method of Forming Resist Pattern>

A method of forming a resist pattern according to the present embodimentincludes:

(1) applying a photoresist composition on a substrate to form a resistfilm on the substrate;

(2) applying the liquid immersion upper layer film forming resincomposition on the resist film to form a liquid immersion upper layerfilm on the resist film;

(3) performing liquid immersion exposure on the resist film on which theliquid immersion upper layer film is formed; and

(4) developing the resist film after the liquid immersion exposure.

According to the resist pattern forming method, since the resist upperlayer film forming resin composition is used, a resist upper layer film(in particular, a liquid immersion upper layer film) being excellent indevelopment liquid solubility while exhibiting a high water repellencycan be formed.

Hereinafter, each step will be described.

(Step (1))

In the step (1), a photoresist composition is applied onto a substrateso as to form a resist film. As the substrate, typically, a siliconwafer, a silicon wafer covered with aluminum, or the like is used. Also,in order to draw out the characteristics of the resist film to themaximum extent, it is also preferable to form an organic or inorganicreflection preventive film, which is disclosed, for example, inJP-B-06-12452, on a surface of the substrate in advance.

The type of the photoresist composition is not particularly limited, anda suitable one may be selected and used from among the photoresistcompositions that are conventionally used for forming a resist film, inaccordance with the purpose of use of the resist. Among these, aphotoresist composition containing a resin P having an acid-dissociativegroup and an acid generating agent Q is preferable.

In the resin P, a structural unit having an acid-dissociative group(hereinafter also referred to as “structural unit (p)”) may be, forexample, a structural unit represented by the following Formula (6).

In the Formula (6), R^(P) is a hydrogen atom, a fluorine atom, a methylgroup, or a trifluoromethyl group. R^(p1) is a monovalent chainhydrocarbon group having one to ten carbon atoms. R^(p2) and R^(p3) eachrepresent a monovalent chain hydrocarbon group having one to ten carbonatoms, a monovalent alicyclic hydrocarbon group having three to twentycarbon atoms, or a ring structure formed by bonding of these groups witheach other and having three to twenty carbon atoms.

The above R^(P) is preferably a hydrogen atom or a methyl group, morepreferably a methyl group, in view of copolymerizability of the monomersgiving the structural units (p) and the like.

Examples of the monovalent chain hydrocarbon group having one to tencarbon atoms represented by the above R^(p1), R^(p2), and R^(p3) includealkyl groups such as methyl group, ethyl group, n-propyl group, i-butylgroup, and n-butyl group.

Examples of the monovalent alicyclic hydrocarbon group having three totwenty carbon atoms represented by the above R^(p2) and R^(p3) includemonocyclic cycloalkyl groups such as cyclobutyl group, cyclopentylgroup, and cyclohexyl group; and polycyclic cycloalkyl groups such asnorbornyl group and adamantyl group.

Examples of the above ring structure formed by bonding of these groupswith each other and having three to twenty carbon atoms includemonocyclic cycloalkane structures such as a cyclopentane structure and acyclohexane structure; and polycyclic cycloalkane structures such as anorbornane structure and an adamantane structure.

Examples of the structural unit (p) include structural units derivedfrom 1-alkyl-1-monocyclic cycloalkyl (meth) acrylates such as1-ethyl-1-cyclopentyl (meth) acrylate; and 2-alkyl-2-polycycliccycloalkyl (meth)acrylates such as 2-i-propyl-2-adamantyl(meth)acrylate.

Besides the structural unit (p), the resin P preferably further has astructural unit (which may hereafter be also referred to as “structuralunit (q)”) containing at least one kind selected from the groupconsisting of a lactone structure, a cyclic carbonate structure, and asultone structure.

Examples of the structural unit (q) include structural units derivedfrom (meth)acrylic acid esters including a norbornane lactone structure,a butyrolactone structure, and others as the lactone structure; anethylene carbonate structure, a propylene carbonate structure, andothers as the cyclic carbonate structure; and a norbornane sultonestructure and a propane sultone structure as the sultone structure.

Also, the resin P may contain other structural units other than thestructural unit (p) and the structural unit (q). Examples of the otherstructural units include a structural unit containing a hydrocarbongroup having four or more and twenty or less carbon atoms and astructural unit containing a polar group such as a hydroxyl group.

The content of the structural unit (p) is preferably 30 mol % to 60 mol% relative to the total structural units constituting the resin P. Bysetting the content of structural unit (p) to be within theaforementioned range, the resolution of the photoresist composition canbe improved. When the content of structural unit (p) is less than theabove lower limit, the pattern formability of the photoresistcomposition may deteriorate. When the content of structural unit (p)exceeds the above upper limit, the adhesion of the formed resist film tothe substrate may decrease.

The content of the structural unit (q) is preferably 20 mol % to 60 mol% relative to the total structural units constituting the resin P. Bysetting the content of structural unit (q) to be within theaforementioned range, the solubility of the resist film formed from thephotoresist composition to the development liquid can be suitablyadjusted, and the adhesion of the resist film to the substrate can beimproved. When the content of structural unit (q) is less than the abovelower limit, the adhesion of the photoresist composition to thesubstrate may decrease. When the content of structural unit (q) exceedsthe above upper limit, the pattern formability of the photoresistcomposition may deteriorate.

The content of the aforementioned other structural units is preferably20 mol % or less, more preferably 15 mol % or less, relative to thetotal structural units constituting the resin P.

The aforementioned acid generating agent Q is a substance that generatesan acid by radiation (exposure). By action of this generated acid, theacid-dissociative group that has protected the carboxyl group and thelike of the resin P is dissociated at the exposed part, therebygenerating a carboxyl group and the like. As a result of this, thesolubility of the resin P to the development liquid changes at theexposed part, whereby the resist pattern is formed.

Examples of the acid generating agent Q include onium salts such assulfonium salt, tetrahydrothiophenium salt, iodonium salt, phosphoniumsalt, diazonium salt, and pyridinium salt, N-sulfonyloxyimide compounds,halogen-containing compounds, and diazoketone compounds.

Examples of the sulfonium salt include triphenylsulfoniumnonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfoniumnonafluoro-n-butanesulfonate, triphenylsulfonium2-(bicyclo[2.2.1]hepta-2′-yl)-1,1,2,2-tetrafluoroethanesulfonate, andtriphenylsulfonium2-(bicyclo[2.2.1]hepta-2′-yl)-1,1-difluoroethanesulfonate.

Examples of the tetrahydrothiophenium salt include1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiopheniumnonafluoro-n-butanesulfonate and1-(4-n-butoxynaphthyl)tetrahydrothiophenium2-(bicyclo[2.2.1]hepta-2′-yl)-1,1,2,2-tetrafluoroethanesulfonate.

The photoresist composition may contain other components such as an aciddiffusion controlling agent R, a resin S containing a fluorine atom in alarger amount per unit mass than in the resin P(fluorine-atom-containing polymer), and a surfactant besides the resin Pand the acid generating agent Q. Examples of the acid diffusioncontrolling agent R include amine compounds such as trioctylamine andtriethanolamine; N-t-alkoxycarbonyl-containing amide compounds such asR-(+)-(t-butoxycarbonyl)-2-piperidinemethanol andN-t-butoxycarbonyl-4-hydroxypiperidine; and photodegradable bases suchas triphenylsulfonium 10-camphorsulfonate and triphenylsulfoniumsalicylate.

The resin S which is a fluorine-atom-containing polymer is a resincontaining a fluorine atom in a larger content per unit mass than thecontent of a fluorine atom per unit mass in the resin P. The resin Scontains a fluorine atom in a larger content per unit mass than thecontent of a fluorine atom per unit mass in the resin P, so that, owingto the oil-repellent characteristic thereof, thefluorine-atom-containing polymer is liable to be locally distributed inthe resist film surface layer when the resist film is formed. As aresult of this, the components in the resist film can be prevented frommigrating into the upper layer film. Also, use of a resin having alater-described alkali-dissociative group as the resin S can enhance thesolubility to the development liquid and can contribute to thesuppression of the residue defects.

A lower limit of the amount of fluorine atoms contained per unit mass inthe resin S is preferably 1 mass %, more preferably 2 mass %, and stillmore preferably 3 mass %. An upper limit of the amount of fluorine atomscontained per unit mass in the resin S is preferably 60 mass %, morepreferably 50 mass %, and still more preferably 40 mass %. By settingthe amount of fluorine atoms contained per unit mass in the resin S tobe within the aforementioned range, the local distribution of the resinS in the resist film can be adjusted more suitably. Here, the amount offluorine atoms contained per unit mass in the resin can be determined bydetermining the structure of the resin through ¹³C-NMR spectrummeasurement and making calculations from the structure.

The form by which the fluorine atoms are contained in the resin S is notparticularly limited, so that the fluorine atoms may be bonded to any ofthe main chain, side chain, and terminal end; however, the resin Spreferably has a structural unit containing a fluorine atom (which mayhereafter be also referred to as “structural unit (f)”). Besides thestructural unit (f), the resin S preferably has a structural unitcontaining an acid-dissociative group in view of improving suppressionof the development defects of the photoresist composition. Thestructural unit containing an acid-dissociative group may be, forexample, the structural unit (p) in the resin P.

Also, the resin S preferably has an alkali-dissociative group. When theresin S has an alkali-dissociative group, the resist film surface can beeffectively turned from being hydrophobic to being hydrophilic whenalkali development is carried out, thereby further improving suppressionof the development defects of the photoresist composition. The“alkali-dissociative group” is a group that substitutes for a hydrogenatom of a carboxyl group, a hydroxyl group, or the like and that isdissociated in an aqueous alkali solution (for example, aqueous solutionof 2.38 mass % tetramethylammonium hydroxide of 23° C.).

The structural unit (f) is preferably a structural unit represented bythe following Formula (f-1) (which may hereafter also be referred to as“structural unit (f-1)”) or a structural unit represented by thefollowing Formula (f-2) (which may hereafter also be referred to as“structural unit (f-2)”). The structural unit (f) may have one kind ortwo or more kinds of each of the structural unit (f-1) and thestructural unit (f-2).

[Structural Unit (f-1)]

The structural unit (f-1) is a structural unit represented by thefollowing Formula (f-1). When the resin S contains the structural unit(f-1), the amount of fluorine atoms contained per unit mass can beadjusted.

In the above Formula (f-1), R^(J) is a hydrogen atom, a fluorine atom, amethyl group, or a trifluoromethyl group. G is a single bond, an oxygenatom, a sulfur atom, —COO—, —SO₂NH—, —CONH—, or —OCONH—. R^(K) is amonovalent fluorinated chain hydrocarbon group having one to six carbonatoms or a monovalent fluorinated alicyclic hydrocarbon group havingfour to twenty carbon atoms.

The above R^(J) is preferably a hydrogen atom or a methyl group, morepreferably a methyl group, in view of copolymerizability of the monomersgiving the structural unit (f-1).

G is preferably —COO—, —SO₂NH—, —CONH—, or —OCONH—, more preferably—COO—.

Examples of the monovalent fluorinated chain hydrocarbon group havingone to six carbon atoms represented by the above R^(K) include a groupin which a part or whole of the hydrogen atoms that the straight-chainor branched-chain alkyl group having one to six carbon atoms has aresubstituted with fluorine atoms.

Examples of the monovalent fluorinated alicyclic hydrocarbon grouphaving four to twenty carbon atoms represented by the above R^(K)include a group in which a part or whole of the hydrogen atoms that themonocyclic or polycyclic hydrocarbon group having four to twenty carbonatoms has are substituted with fluorine atoms.

R^(K) is preferably a fluorinated chain hydrocarbon group, morepreferably 2,2,2-trifluoroethyl group or 1,1,1,3,3,3-hexafluoro-2-propylgroup, and still more preferably 2,2,2-trifluoroethyl group.

When the resin S has the structural units (f-1), a lower limit of thecontent of the structural unit (f-1) is preferably 10 mol %, morepreferably 20 mol %, relative to the total structural units constitutingthe resin S. An upper limit of the content is preferably 100 mol %, morepreferably 90 mol %. By setting the content of the structural unit (f-1)to be within the aforementioned range, the amount of the fluorine atomscontained in the resin S per unit mass can be more suitably adjusted.

[Structural Unit (f-2)]

The structural unit (f-2) is represented by the following Formula (f-2).When the resin S contains the structural unit (f-2), the solubility tothe alkali development liquid is improved, and generation of developmentdefects can be suppressed.

The structural unit (f-2) can be roughly classified into two, that are,(x) one having an alkali-soluble group and (y) one having a group thatis dissociated by action of an alkali to increase the solubility to thealkali development liquid (which may hereafter be also referred to as“alkali-dissociative group”). In both of the cases (x) and (y), in theabove Formula (f-2), R^(C) is a hydrogen atom, a fluorine atom, a methylgroup, or a trifluoromethyl group. R^(D) is a single bond, a(s+1)-valent hydrocarbon group having one to twenty carbon atoms, astructure in which an oxygen atom, a sulfur atom, —NR^(dd)—, a carbonylgroup, —COO—, or —CONH— is bonded to the terminal end on the R^(E) sideof this hydrocarbon group, or a structure in which a part of thehydrogen atoms that this hydrocarbon group has are substituted with anorganic group having a heteroatom. R^(dd) is a hydrogen atom or amonovalent hydrocarbon group having one to ten carbon atoms. Also, s isan integer of 1 to 3. However, when s is 1, R^(D) in no cases is asingle bond.

When the structural unit (f-2) is (x) one having an alkali-solublegroup, R^(F) is a hydrogen atom, and A¹ is an oxygen atom, —COO—*, or—SO₂O—*. The symbol * denotes the site bonded to R^(F). W is a singlebond, a hydrocarbon group having one to twenty carbon atoms, or adivalent fluorinated hydrocarbon group. When A¹ is an oxygen atom, W¹ isa fluorinated hydrocarbon group having a fluorine atom or a fluoroalkylgroup at the carbon atom bonded to A¹. R^(E) is a single bond or adivalent organic group having one to twenty carbon atoms. When s is 2 or3, the plurality of R^(E), W¹, A¹, and R^(F) may each be the same ordifferent. When the structural unit (f-2) has (x) an alkali-solublegroup, the affinity to the alkali development liquid is enhanced, anddevelopment defects can be suppressed. The structural unit (f-2) having(x) an alkali-soluble group is particularly preferably a structural unitin which A¹ is an oxygen atom, and W¹ is1,1,1,3,3,3-hexafluoro-2,2-methanediyl group.

When the structural unit (f-2) is (y) one having an alkali-dissociativegroup, R^(F) is a monovalent organic group having one to thirty carbonatoms, and A¹ is an oxygen atom, —NR^(aa)—, —COO—*, or —SO₂O—*. R^(aa)is a hydrogen atom or a monovalent hydrocarbon group having one to tencarbon atoms. The symbol * denotes the site bonded to R^(F). W¹ is asingle bond or a divalent fluorinated hydrocarbon group having one totwenty carbon atoms. R^(E) is a single bond or a divalent organic grouphaving one to twenty carbon atoms. When A¹ is —COO—* or —SO₂O—*, then W¹or R^(F) has a fluorine atom at the carbon atom bonded to A¹ or a carbonatom adjacent thereto. When A¹ is an oxygen atom, W¹ and R^(E) are asingle bond; R^(D) is a structure in which a carbonyl group is bonded tothe terminal end on the R^(E) side of the hydrocarbon group having oneto twenty carbon atoms; and R^(F) is an organic group having a fluorineatom. When s is 2 or 3, the plurality of R^(E), W¹, A¹, and R^(F) mayeach be the same or different. When the structural unit (f-2) has (y) analkali-dissociative group, the resist film surface is turned from beinghydrophobic to being hydrophilic in the alkali development step. As aresult of this, the affinity to the development liquid is greatlyenhanced, and development defects can be more efficiently suppressed.The structural unit (f-2) having (y) an alkali-dissociative group isparticularly preferably a structural unit in which A¹ is —COO—*, and oneor both of R^(F) and W¹ have a fluorine atom.

R^(C) is preferably a hydrogen atom or a methyl group, more preferably amethyl group, in view of copolymerizability of the monomers giving thestructural unit (f-2), or the like.

When R^(E) is a divalent organic group, a group having a lactonestructure is preferable; a group having a polycyclic lactone structureis more preferable; and a group having a norbornane lactone structure isstill more preferable.

When the resin S has the structural unit (f-2), a lower limit of thecontent of the structural unit (f-2) is preferably 0.1 mol %, morepreferably 5 mol %, relative to the total structural units constitutingthe resin S. An upper limit of the content is preferably 50 mol %, morepreferably 40 mol %. By setting the content of the structural unit (f-2)to be within the aforementioned range, the resist film surface formedfrom the photoresist composition can be more suitably changed from beingwater-repellent to being hydrophilic between before and after the alkalidevelopment.

A lower limit of the content of the structural unit (f) is preferably 10mol %, more preferably 20 mol %, and still more preferably 25 mol %,relative to the total structural units constituting the resin S. Anupper limit of the content is preferably 100 mol %, more preferably 90mol %, and still more preferably 80 mol %.

A lower limit of the content of the structural unit containing anacid-dissociative group in the resin S is preferably 10 mol %, morepreferably 20 mol %, and still more preferably 25 mol %, relative to thetotal structural units constituting the resin S. An upper limit of thecontent is preferably 90 mol %, more preferably 80 mol %, and still morepreferably 75 mol %. By setting the content of the structural unitcontaining an acid-dissociative group to be within the aforementionedrange, suppression of the development defects of the photoresistcomposition can be further improved.

When the photoresist composition contains the resin S, a lower limit ofthe content of the resin S is preferably 0.1 part by mass, morepreferably 0.5 part by mass, still more preferably 1 part by mass, andparticularly preferably 2 parts by mass, relative to 100 parts by massof the resin P. An upper limit of the above content is preferably 30parts by mass, more preferably 20 parts by mass, still more preferably15 parts by mass, and particularly preferably 10 parts by mass. Thephotoresist composition may contain one kind or two or more kinds of theresin S.

The resin S can be synthesized by a method similar to that of theabove-described resin P.

A lower limit of Mw of the resin S by GPC is preferably 1,000, morepreferably 3,000, still more preferably 4,000, and particularlypreferably 5,000. An upper limit of the above Mw is preferably 50,000,more preferably 30,000, still more preferably 20,000, and particularlypreferably 10,000. By setting the Mw of the resin S to be within theaforementioned range, the application property of the photoresistcomposition and the suppression of the development defects are improved.

A lower limit of the ratio (Mw/Mn) of Mw to Mn of the resin S by GPC istypically 1, preferably 1.2. An upper limit of the above ratio ispreferably 5, more preferably 3, and still more preferably 2.

The photoresist composition is prepared, for example, by dissolving theaforementioned resin P, acid generating agent Q, and optional aciddiffusion controlling agent R and the like in accordance with the needsinto a solvent. Also, the photoresist composition is used typicallyafter being filtrated through a filter having a pore diameter of about30 nm. The total solid component concentration of the photoresistcomposition is preferably 0.2 mass % to 20 mass % in view of thefacility in application.

As an application method of the photoresist composition, aconventionally known application method such as rotation application,cast application, or roll application may be used. After the photoresistcomposition is applied onto the substrate, the substrate may bepre-baked (PB) in order to volatilize the solvent.

(Step (2))

In the step (2), the resist upper layer film forming resin compositionis applied onto the resist film to form a liquid immersion upper layerfilm. As an application method of the upper layer film composition, amethod similar to the application method of the photoresist compositionin the step (1) may be used. In the present step, the substrate ispreferably pre-baked (PB) after the upper layer film composition isapplied. By forming a liquid immersion upper layer film on the resistfilm in this manner, the liquid immersion medium and the resist film areprevented from being in direct contact with each other, whereby decreasein the lithography performance of the resist film caused by penetrationof the liquid medium into the resist film and contamination of the lensof the projection exposure apparatus by the components eluted from theresist film to the liquid medium are effectively suppressed.

The thickness of the formed liquid immersion upper layer film ispreferably approximated to the odd-number times of λ/4 m (here, λ is thewavelength of radiation, and m is the refractive index of the upperlayer film) as much as possible. By doing so, the effect of suppressingreflection on the upper side interface of the resist film can beenlarged.

(Step (3))

In the step (3), the liquid immersion medium is placed on the liquidimmersion upper layer film, and the resist film is subjected to liquidimmersion exposure via this liquid immersion medium.

As the liquid immersion medium, a liquid having a higher refractiveindex than that of air is typically used. Water is preferably used asthe liquid immersion medium, and pure water is more preferably used.Here, in accordance with the needs, the pH of the liquid immersionmedium may be adjusted. An exposure light is radiated from the exposureapparatus in a state in which this liquid immersion medium isinterposed, that is, in a state in which the gap between the lens of theexposure apparatus and the liquid immersion upper layer film is filledwith the liquid immersion medium, so as to expose the liquid immersionupper layer film and the photoresist film via a mask having apredetermined pattern.

The exposure light used in this liquid immersion exposure can besuitably selected in accordance with the type of the photoresist filmand the liquid immersion upper layer film, and examples thereof includevisible light; ultraviolet rays such as a g-beam and an i-beam; farinfrared rays such as an excimer laser; an X-ray such as a synchrotronradiation beam; and a charged particle beam such as an electron beam.Among these, an ArF excimer laser beam (wavelength of 193 nm) and a KrFexcimer laser beam (wavelength of 248 nm) are preferable, and an ArFexcimer laser beam is more preferable. Also, the conditions forradiation of the exposure light, for example, the exposure amount andthe like, may be suitably set in accordance with the blendingcomposition of the photoresist composition and the resist upper layerfilm forming resin composition, the type of the additives contained inthese, and the like.

After the above liquid immersion exposure, the substrate is preferablysubjected to post-exposure baking (PEB) in order to improve theresolution, the pattern shape, the development properties, and the likeof the resulting resist pattern. The PEB temperature can be suitably setin accordance with the type and the like of the photoresist compositionand the resist upper layer film forming resin composition that are putto use; however, the PEB temperature is typically 30° C. to 200° C.,preferably 50° C. to 150° C. The PEB time is typically 5 seconds to 600seconds, preferably 10 seconds to 300 seconds.

(Step (4))

In the step (4), the resist film subjected to the above liquid immersionexposure is developed. This can yield a desired resist pattern.According to the method of forming the resist pattern, the liquidimmersion upper layer film is formed by using the upper layer filmcomposition, so that the liquid immersion upper layer film can be easilyremoved by the development liquid during the development or by thewashing liquid during the washing when washing is carried out after thedevelopment. In other words, there is no need of a separate peeling stepfor removing the liquid immersion upper layer film. In the present step,either alkali development or organic solvent development may be carriedout. By the alkali development, a positive-type resist pattern isobtained. By the organic solvent development, a negative-type resistpattern is obtained. Among these, the alkali development is preferable.

When the alkali development is performed, the development liquid ispreferably an alkaline aqueous solution in which at least one kind ofalkaline compounds such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine,n-propylamine, diethylamine, di-n-propylamine, triethylamine,methyldiethylamine, dimethylethanolamine, triethanolamine,tetraalkylammonium hydroxides (for example, tetramethylammoniumhydroxide (TMAH), tetraethylammonium hydroxide, and the like), pyrrole,piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and1,5-diazabicyclo-[4.3.0]-5-nonane is dissolved. Among these, an aqueoussolution of tetraalkylammonium hydroxides is preferable, and an aqueoussolution of TMAH is more preferable.

A suitable amount of a water-soluble organic solvent such as an alcoholsuch as methanol or ethanol, or a surfactant, for example, may be addedinto the development liquid in the above alkali development.

Also, in the case of the organic solvent development, a developmentliquid containing an organic solvent is used. The organic solvent maybe, for example, one similar to the solvent exemplified as the solventcontained in the resist upper layer film forming resin compositiondescribed above. Among these, an ether-based solvent, a ketone-basedsolvent, and an ester-based solvent are preferable, and n-butyl acetate,isopropyl acetate, amyl acetate, anisole, 2-butanone, methyl-n-butylketone, and methyl-n-amyl ketone are more preferable. One kind or two ormore kinds of these organic solvents may be used.

The content of the organic solvent in the development liquid for theorganic solvent development is preferably 80 mass % or more, morepreferably 90 mass % or more, and still more preferably 100 mass %. Bysetting the content of the organic solvent in the development liquid tobe within the aforementioned range, the dissolution contrast between theexposed part and the non-exposed part can be improved and, as a resultof this, a resist pattern excellent in lithography characteristics canbe formed. Examples of the components other than the organic solventinclude water and silicone oil.

The resist film subjected to the above development is preferably washedwith use of a rinsing liquid and dried. As the rinsing liquid, water ispreferable in the case of the alkali development, and ultrapure water ismore preferable. In the case of the organic solvent development, anorganic solvent is preferable as the rinsing liquid, and analcohol-based solvent is more preferable.

<Development Modifier>

The development modifier of the present embodiment contains theaforementioned resin composition. The effect of suppressing the residuedefects by the resist upper layer film forming resin compositionaccording to one embodiment of the present invention derives from thefact that the highly acidic resin contained in the resin composition andthe resist film form a mixing layer, so that the aforementioned resincomposition can be used as the development modifier in a process otherthan the liquid immersion exposure process. The higher the wiringdensity is, the larger the influence of the presence or absence of theresidue defects on the product quality is. By using the developmentmodifier containing the aforementioned resin composition in an extremeultraviolet ray (EUV) or electron beam (EB) exposure process, the yieldcan be improved. In particular, when the resist film contains afluorine-containing polymer, dissolution of the fluorine-containingpolymer having a relatively lower solubility to the alkali developmentliquid can be promoted when the development modifier forms a mixinglayer, so that a higher effect is expected in suppressing the residuedefects.

Details of the resin composition contained in the development modifier,the preparation method thereof, and the method of forming the resistpattern are basically the same as in the case of the aforementionedresist upper layer film forming resin composition. Hereafter, only thedifferent parts will be described.

<Method of Forming Resist Pattern>

A method of forming a resist pattern according to the present embodimentincludes:

applying a photoresist composition on a substrate to form a resist filmon the substrate;

exposing the resist film; and

developing the exposed resist film with an alkali development liquid,

and further includes applying the development modifier of the presentembodiment on a surface of the resist film after the resist film isformed and before the exposed resist film is developed.

In the present forming method, the development modifier can be appliedto a dry exposure process other than the liquid immersion exposureprocess. The resist film forming step, the exposure process, and thedevelopment step are the same as in the mode of using the upper layerfilm composition except that the liquid immersion exposure process isnot used and that a radiation beam having a wavelength of 50 nm or lesssuch as an EUV (extreme ultraviolet ray, wavelength: 13.5 nm) can beused as the exposure light in the exposure step.

In the present embodiment, the method further includes a step ofapplying the development modifier of the present embodiment on a surfaceof the resist film after the step of forming the resist film and beforethe step of developing the exposed resist film. The development modifierapplication step can be carried out irrespective of whether thedevelopment modifier application step is carried out before or after theexposure step, provided that the development modifier application iscarried out between the resist film forming step and the developmentstep. The application step is preferably carried out before the exposurestep from the viewpoint of production efficiency and maintaining thestate of the resist film after the exposure. As the application method,a procedure similar to that of the method for applying the upper layerfilm composition can be adopted.

EXAMPLES

Hereafter, the present invention will be described in detail by usingExamples; however, the present invention is not limited to the followingExamples unless the gist thereof is surpassed.

(¹³C-Nmr Analysis)

The ¹³C-NMR analysis was carried out using: a nuclear magneticresistance apparatus (JNM-ECX400 manufactured by JEOL Ltd.); CDCl₃ as ameasurement solvent; and tetramethylsilane (TMS) as an internalreference.

(Mw and Mn Measurement)

The Mw and Mn of the resin were measured by gel permeationchromatography (GPC) under the following conditions.

GPC column: two columns of G2000HXL, one column of G3000HXL, and onecolumn of G4000HXL (manufactured by Tosoh Corporation)

Elution solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Column temperature: 40° C.

Reference material: monodispersed polystyrene

Detector: differential refractometer

<Synthesis of Resin 1 for Photoresist Composition>

The monomers (M-1) to (M-3) represented by the following formula wereused in synthesizing the resin 1.

Synthesis Example 1

Into 200 g of 2-butanone, 53.93 g (50 mol %) of the compound (M-1),35.38 g (40 mol %) of the compound (M-2), and 10.69 g (10 mol %) of thecompound (M-3) were dissolved, and further, 5.58 g of dimethyl2,2′-azobis(2-methylpropionate) was put to prepare a monomer solution. Athree-neck flask of 500 mL into which 100 g of 2-butanone had been putwas purged with nitrogen for 30 minutes. After purging with nitrogen,the reaction tank was heated to 80° C. while stirring, and the abovemonomer solution prepared in advance was dropwise added with use of adropping funnel over three hours. Assuming that the start of dropwiseaddition was the start of polymerization, the polymerization reactionwas carried out for six hours. After the polymerization ended, thepolymerization solution was cooled with water to a temperature of 30° C.or lower and put into 2,000 g of methanol, so as to filtrate thedeposited white powder. The filtrated white powder was washed for twotimes each with use of 400 g of methanol into a slurry form, thereafterfiltrated, and dried at 50° C. for 17 hours to obtain a white powderresin 1 (74 g, yield of 74%).

This resin 1 was a copolymer in which Mw was 6,900; Mw/Mn was 1.70; andthe content ratio of each of the structural units derived from thecompound (M-1), the compound (M-2), and the compound (M-3) was53.0:37.2:9.8 (mol %) as a result of ¹³C-NMR analysis. Here, the contentof the low-molecular-weight components derived from each monomer in thepolymer was 0.03 mass % relative to 100 mass % of the polymer.

<Preparation of Photoresist Composition 1>

A mixture was prepared using 100 parts by mass of the resin 1, 1.5 partsby mass of triphenylsulfonium nonafluoro-n-butanesulfonate and 6 partsby mass of 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiopheniumnonafluoro-n-butanesulfonate as an acid generating agent, and 0.65 partby mass of R-(+)-(tert-butoxycarbonyl)-2-piperidinemethanol as an aciddiffusion controlling agent. Into this mixture, 2,900 parts by mass ofpropylene glycol monomethyl ether acetate, 1,250 parts by mass ofcyclohexanone, and 100 parts by mass of γ-butyrolactone as solvents wereadded and prepared, followed by filtration with a filter having a porediameter of 30 nm to prepare a photoresist composition 1.

<Synthesis of Resins A to C in Resist Upper Layer Film Forming ResinComposition>

The monomers (M-5) to (M-10) represented by the following formula wereused in synthesizing the resins A to C.

(Synthesis Example 2: Synthesis of Resin (A-1))

6.2 g of the compound (M-5), 15.9 g of the compound (M-6), and 7.9 g ofthe compound (M-9) as well as 3.6 g of 2,2-azobis (methyl2-methylisopropionate) as a polymerization initiator were dissolved into30 g of isopropanol to prepare A monomer solution. On the other hand, 30g of isopropanol was put into a three-neck flask of 200 mL equipped witha thermometer and a dropping funnel, and the flask was purged withnitrogen for 30 minutes. After the purging with nitrogen, the inside ofthe flask was heated to attain a temperature of 80° C. while stirringwith a magnetic stirrer, and the monomer solution prepared in advancewas dropwise added with use of the dropping funnel over three hours.After the dropwise addition ended, the reaction was further continuedfor three hours. By cooling to attain 30° C. or lower, a polymerizationreaction liquid was obtained. The polymerization liquid was concentratedto attain 60 g, and 60 g of methanol and 360 g of n-hexane were put intothe concentrated liquid and put into a separation funnel, so as toperform separation purification. After the separation, the lower layerwas collected. The collected lower layer liquid was substituted with4-methyl-2-pentanol; the whole amount was adjusted to 256 g; andseparation purification with 128 g of methanol and 256 g of pure waterwas carried out, so as to collect 280 g of the upper layer. To thisupper layer, 140 g of 2-butanone and 280 g of pure water were added andstirred for 30 minutes. Thereafter, 400 g of the upper layer wascollected and substituted with 4-methyl-2-pentanol, so as to obtain asolution containing the resin (A-1) (yield of 52%).

In the obtained resin (A-1), Mw was 4,500 and Mw/Mn was 1.6. Thecontents of the respective structural units derived from (M-5), (M-6),and (M-9) were 30 mol %, 62 mol %, and 8 mol %, respectively, as aresult of ¹³C-NMR analysis.

(Synthesis Examples 3 to 7: Synthesis of Resins (A-2) to (A-3) andResins (B-1) to (B-3))

The resins (A-2) to (A-3) and the resins (B-1) to (B-3) were synthesizedby a procedure similar to that of the resin (A-1) except that themonomers were blended to attain a composition shown in Table 1.

(Synthesis Example 8: Synthesis of Resin (C-1))

50 g of the compound (M-8) and 1.95 g of 2,2-azobis (methyl2-methylisopropionate) were dissolved into 50 g of 2-butanone to preparea monomer solution in advance. On the other hand, 50 g of 2-butanone wasput into a three-neck flask of 500 mL equipped with a thermometer and adropping funnel, and the flask was purged with nitrogen for 30 minutes.After the purging with nitrogen, the inside of the flask was heated toattain a temperature of 80° C. while stirring with a magnetic stirrer,and the monomer solution prepared in advance was dropwise added with useof the dropping funnel over two hours. After the dropwise additionended, the reaction was further continued for two hours, and 1.17 g of2,2-azobis (methyl 2-methylisopropionate) was further added, so as tocontinue the reaction for further two hours. By cooling to attain 30° C.or lower, a polymerization reaction liquid was obtained. Subsequently,the obtained polymerization liquid was transferred to a separationfunnel, and 50 g of methanol and 600 g of n-hexane were put into theseparation funnel, so as to perform separation purification. After theseparation, the lower layer was collected. The lower layer liquid wasdiluted with 2-butanone to attain 100 g, and the resultant wastransferred again to the separation funnel. Into the separation funnel,50 g of methanol and 600 g of n-hexane were put, and the separationpurification was carried out again. After the separation, the lowerlayer was collected. The collected lower layer liquid was substitutedwith 4-methyl-2-pentanol; the whole amount was adjusted to 250 g; andseparation purification with 250 g of water was carried out, so as tocollect the upper layer, which was then substituted with4-methyl-2-pentanol again, so as to obtain a solution containing theresin (C-1) (yield of 77%).

In the resin (C-1), Mw was 12,130 and Mw/Mn was 1.65.

(Synthesis Example 9: Synthesis of Resin (C-2))

25.0 g of 2,2-azobis (methyl 2-methylisopropionate) as a polymerizationinitiator was dissolved into 25.0 g of 2-butanone to prepare apolymerization initiator solution. On the other hand, 166.4 g (50 mol %)of the compound (M-8), 133.6 g (50 mol %) of the compound (M-10), and575.0 g of 2-butanone were put into a three-neck flask of 2,000 mLequipped with a thermometer and a dropping funnel, and the flask waspurged with nitrogen for 30 minutes. After the purging with nitrogen,the inside of the flask was heated to attain a temperature of 80° C.while stirring with a magnetic stirrer. Next, the preparedpolymerization initiator solution was dropwise added in five minuteswith use of the dropping funnel and aged for 6 hours. Thereafter, theresultant was cooled to 30° C. or lower to obtain a polymerizationreaction liquid. Subsequently, the obtained polymerization reactionliquid was concentrated to 600 g and then transferred to a separationfunnel. Into this separation funnel, 193 g of methanol and 1,542 g ofn-hexane were put, so as to perform separation purification. After theseparation, the lower layer liquid was collected. Into the lower layerliquid, 117 g of 2-butanone and 1,870 g of n-hexane were put, so as toperform separation purification. After the separation, the lower layerliquid was collected. Further, 93 g of methanol, 77 g of 2-butanone, and1,238 g of n-hexane were put into the collected lower layer liquid, soas to perform separation purification. After the separation, the lowerlayer liquid was collected. The collected lower layer liquid wassubstituted with 4-methyl-2-pentanol, and this solution was washed withdistilled water and substituted with 4-methyl-2-pentanol again, so as toobtain a solution containing the resin (C-2) (yield of 79%).

In the resin (C-2), Mw was 7,700 and Mw/Mn was 1.61. The contents of therespective structural units derived from (M-8) and (M-10) were 51 mol %and 49 mol %, respectively, as a result of ¹³C-NMR analysis.

(Synthesis Example 10: Synthesis of Resin (C-3))

The resin (C-3) was synthesized by a procedure similar to that of theresin (C-2) except that the monomers were blended to attain acomposition shown in Table 1.

TABLE 1 Amount of fluorine atoms Monomers per unit Physical propertyContent Content Content mass Yield values Resin Type (mol %) Type (mol%) Type (mol %) (mass %) (%) Mw Mw/Mn Synthesis Example 2 Resin A-1 M-530 M-6 62 M-9  8 0 52 4,500 1.60 Synthesis Example 3 Resin A-2 M-5 72M-8 18 M-9 10 17.6 57 4,100 1.65 Synthesis Example 4 Resin A-3 M-7 90M-9 10 — — 0 55 4,400 1.59 Synthesis Example 5 Resin B-1 M-5 30 M-6 68M-9  2 0 72 8,250 1.55 Synthesis Example 6 Resin B-2 M-8 98 M-9 2 — — 3879 7,950 1.50 Synthesis Example 7 Resin B-3 M-7 96 M-9 4 — — 0 76 7,6501.52 Synthesis Example 8 Resin C-1 M-8 100 — — — — 38.3 77 12,130 1.65Synthesis Example 9 Resin C-2 M-8 51 M-10 49 — — 42.8 79 7,700 1.61Synthesis Example 10 Resin C-3 M-8 40 M-10 60 — — 43.9 82 8,600 1.60

<Preparation of Resist Upper Layer Film Composition>

Example 1

A mixture was prepared using 4 parts by mass of the resin (A-1), 76parts by mass of the resin (C-1), and 20 parts by mass of the resin(C-2). Into this mixture, 2,500 parts by mass of 4-methyl-2-pentanol and2,500 parts by mass of diisoamyl ether were added as solvents, followedby filtration with a filter having a pore diameter of 30 nm, so as toprepare a resist upper layer film forming resin composition of theExample 1.

Examples 2 to 11 and Comparative Examples 1 to 2

A resist upper layer film forming resin composition was prepared in thesame manner as in the Example 1 except that the composition shown in thefollowing Table 2 was used.

<Evaluation>

The following items were evaluated with respect to the obtained resistupper layer film forming resin compositions.

(Receding Contact Angle of Water)

The receding contact angle value of water on the upper layer filmsurface was measured. An 8-inch silicon wafer was spin-coated with theresist upper layer film forming resin composition and pre-baked (PB) at90° C. for 60 seconds on a hot plate, thereby to form an upper layerfilm having a film thickness of 30 nm. Thereafter, the receding contactangle was measured by the following procedure quickly in an environmentwith a room temperature of 23° C., a humidity of 45%, and an ordinarypressure with use of a contact angle meter (DSA-10 manufactured byKRUS). First, the wafer stage position of the above contact angle meterwas adjusted, and the above wafer was set on the adjusted stage. Next,water was injected into a needle, and the position of the needle wasfinely adjusted to an initial position at which a water droplet could beformed on the above set wafer. Thereafter, water was discharged fromthis needle, and a water droplet of 25 μL was formed on the wafer. Then,the needle was temporarily drawn out from the water droplet, and theneedle was pulled down at the initial position again and placed in thewater droplet. Subsequently, the water droplet was sucked with theneedle for 90 seconds at a speed of 10 μL/min and, at the same time, thecontact angle was measured once per second for a sum of 90 times. Amongthese, an average value of the contact angles for 20 seconds from thetime point at which the measured value of the contact angle becamestable was calculated, so as to determine the receding contact angle(unit: degrees))(°.

(Water Mark Defects, Residue Defects)

The water mark defects and residue defects on the resist patternobtained by exposure/development of the photoresist on which the upperlayer film had been formed were evaluated. A 12-inch silicon watersurface was spin-coated with a lower layer reflection preventive film(ARC66 manufactured by Nissan Chemical Corporation) with use of anapplication/development apparatus (Lithius Pro-i manufactured by TokyoElectron Ltd.) and thereafter pre-baked (PB) to form a lower layerreflection preventive film having a film thickness of 105 nm.Subsequently, with use of the above application/development apparatus,the wafer was spin-coated with each photoresist and pre-baked (PB) at90° C. for 60 seconds, followed by cooling at 23° C. for 30 seconds toform a photoresist film having a film thickness of 90 nm. Thereafter, anupper layer film forming resin composition was applied onto this resistfilm and pre-baked (PB) at 90° C. for 60 seconds to form an upper layerfilm having a film thickness of 30 nm. Next, exposure was carried outvia a mask for forming a pattern with a 45 nm line/90 nm pitch under theoptical conditions with NA: 1.30, Dipole with use of an ArF liquidimmersion exposure apparatus (S610C manufactured by Nikon Corporation).Thereafter, the PIR (washing after exposure) step was omitted, and thewafer was subjected to post-exposure baking (PEB) at 90° C. for 60seconds on a hot plate, followed by cooling at 23° C. for 30 seconds.Thereafter, paddle development was carried out for 10 seconds using a2.38% aqueous solution of TMAH as a development liquid, and the waferwas spin-dried by swinging at 2000 rpm for 15 seconds, so as to obtain asubstrate on which the resist pattern had been formed. The obtainedsubstrate on which the resist pattern had been formed was subjected to adefect test with use of a defect testing apparatus (KLA2810 manufacturedby KLA-Tencor Corporation) and observed with use of a scanning electronmicroscope (RS6000 manufactured by Hitachi High-TechnologiesCorporation), so as to evaluate the water mark defects and residuedefects according to the following evaluation standards.

<Evaluation Standard of Water Mark Defects>

◯: the number of water mark defects was 0 per one wafer

Δ: the number of water mark defects was one or two per one wafer

x: the number of water mark defects was 3 or more per one wafer

<Evaluation Standard of Residue Defects>

◯: the number of residue defects was less than 100 per one wafer

x: the number of residue defects was 100 or more per one wafer

TABLE 2 Resist upper layer film forming composition Evaluation resultsResin A Resin B Resin C Solvent D Receding Content Content ContentContent Contact Water (parts by (parts by (parts by (parts by angle markResidue Type mass) Type mass) Type mass) Type mass) [°] defects defectsExample 1 A-1 4 — — C-1/C-2 76/20 D-1/D-2 2500/2500 81 ∘ ∘ Example 2 A-24 — — C-1/C-2 76/20 D-1/D-2 1000/4000 81 ∘ ∘ Example 3 A-1 2 B-1 18C-1/C-2 60/20 D-1/D-2 2500/2500 80 ∘ ∘ Example 4 A-2 2 B-2 18 C-1/C-260/20 D-1/D-2 1000/4000 80 ∘ ∘ Example 5 A-1 2 B-2 78 C-2 20 D-1/D-22500/2500 81 ∘ ∘ Example 6 A-1 1 B-1 29 C-1/C-3 55/15 D-1/D-2 1000/400084 ∘ ∘ Example 7 A-3 2 B-2 78 C-3 20 D-1/D-2 2500/2500 84 ∘ ∘ Example 8A-1 2 B-3 18 C-1/C-2 60/20 D-1/D-2 2500/2500 81 ∘ ∘ Example 9 A-3 4 B-256 C-1/C-2 20/20 D-1/D-2 2500/2500 81 ∘ ∘ Example 10 A-1 15 B-2 10C-1/C-3 55/20 D-1/D-2 2500/2500 76 Δ ∘ Example 11 A-3 10 B-2 5 C-1/C-365/20 D-1/D-2 2500/2500 77 Δ ∘ Comparative Example 1 A-1 60 — — C-1/C-220/20 D-1/D-2 2500/2500 72 x ∘ Comparative Example 2 B-3 4 C-1/C-2 76/20D-1/D-2 2500/2500 81 ∘ x

From the results of Table 2, it will be understood that a resist upperlayer film excellent in both of residue defect preventability and watermark defect preventability can be formed by using the resist upper layerfilm forming resin composition of the Examples. Here, in the Examples 10and 11, a slight amount of water mark defects were generated. This seemsto be caused by the fact that the content of the highly acidic resin Ain the composition was comparatively large, and the water repellency ofthe obtained upper layer film was decreased a little. From thecomparison between the Examples 3 to 9 and the Examples 10 to 11, it canbe stated that the content of the resin A is preferably smaller than thecontent of the resin B in view of each of the contents of the resin Aand the resin B in the composition. Also, from the comparison betweenthe Examples 1 to 9 and the Examples 10 to 11, it can be stated that thecontent of the resin A in the composition preferably is relativelysmaller as compared with other resins, and is preferably less than 5mass %.

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

What is claimed is:
 1. A method of forming a resist pattern, comprising:applying a photoresist composition on a substrate to form a resist filmon the substrate; applying a resin composition on the resist film toform a liquid immersion upper layer film on the resist film; performingliquid immersion exposure on the resist film on which the liquidimmersion upper layer film is formed; and developing the resist filmafter the liquid immersion exposure, wherein the resin compositioncomprises: a resin A that comprises a sulfonic-acid-group-containingstructural unit in an amount exceeding 5 mol % with respect to totalstructural units included in the resin A, the resin A having a contentof a fluorine atom of 30 mass % or less with respect to a total mass ofthe resin A; a resin C that comprises a fluorine atom in a largercontent per unit mass than the content of a fluorine atom per unit massin the resin A; and a solvent, wherein a content of the resin A in theresin composition is lower than a content of the resin C in the resincomposition in terms of mass, and wherein a content of the resin A in atotal mass of resin solid components of the resin composition is 0.1mass % or more and less than 5 mass %.
 2. The method according to claim1, wherein a content of the resin C in the total mass of resin solidcomponents of the resin composition is 10 mass % or more and 98 mass %or less.
 3. The method according to claim 1, wherein an amount of afluorine atom in the resin A with respect to a total mass of the resin Ais 0 mass % or more and less than 30 mass %, and an amount of a fluorineatom in the resin C with respect to a total mass of the resin C exceeds40 mass %.
 4. The method according to claim 3, wherein the resin A doesnot contain a fluorine atom.
 5. The method according to claim 1, whereinthe resin composition further comprises a resin B that comprises asulfonic-acid-group-containing structural unit in an amount exceeding 0mol % and being 5 mol % or less with respect to total structural unitsincluded in the resin B, the resin B having a content of a fluorine atomper unit mass smaller than the content of a fluorine atom per unit massin the resin C.
 6. The method according to claim 5, wherein thesulfonic-acid-group-containing structural unit in one or both of theresin A and the resin B is represented by formula (1):

wherein in the formula (1), Ra is a hydrogen atom or a methyl group, andRb is a single bond or a divalent organic group.
 7. The method accordingto claim 1, wherein the resin C does not contain asulfonic-acid-group-containing structural unit.
 8. The method accordingto claim 1, wherein the resin A further comprises acarboxyl-group-containing structural unit.
 9. The method according toclaim 1, wherein a receding contact angle of a film formed from theresin composition, with respect to water, is 80° or more.
 10. The methodaccording to claim 1, wherein the sulfonic-acid-group-containingstructural unit in the resin A is represented by formula (1):

wherein in the formula (1), Ra is a hydrogen atom or a methyl group, andRb is a single bond or a divalent organic group.
 11. A method of forminga resist pattern, comprising: applying a photoresist composition on asubstrate to form a resist film on the substrate; exposing the resistfilm; and developing the exposed resist film with an alkali developmentliquid, the method further comprising applying a resin composition on asurface of the resist film after the resist film is formed and beforethe exposed resist film is developed, wherein the resin compositioncomprises: a resin A that comprises a sulfonic-acid-group-containingstructural unit in an amount exceeding 5 mol % with respect to totalstructural units included in the resin A, the resin A having a contentof a fluorine atom of 30 mass % or less with respect to a total mass ofthe resin A; a resin C that comprises a fluorine atom in a largercontent per unit mass than the content of a fluorine atom per unit massin the resin A; and a solvent, wherein a content of the resin A in theresin composition is lower than a content of the resin C in the resincomposition in terms of mass, and wherein a content of the resin A in atotal mass of resin solid components of the resin composition is 0.1mass % or more and less than 5 mass %.
 12. The method according to claim11, wherein the exposing of the resist film is carried out with anextreme ultraviolet ray.
 13. The method according to claim 11, whereinthe photoresist composition comprises a fluorine-atom-containingpolymer.
 14. The method according to claim 11, wherein a content of theresin C in the total mass of resin solid components of the resincomposition is 10 mass % or more and 98 mass % or less.
 15. The methodaccording to claim 11, wherein an amount of a fluorine atom in the resinA with respect to a total mass of the resin A is 0 mass % or more andless than 30 mass %, and an amount of a fluorine atom in the resin Cwith respect to a total mass of the resin C exceeds 40 mass %.
 16. Themethod according to claim 15, wherein the resin A does not contain afluorine atom.
 17. The method according to claim 11, wherein the resincomposition further comprises a resin B that comprises asulfonic-acid-group-containing structural unit in an amount exceeding 0mol % and being 5 mol % or less with respect to total structural unitsincluded in the resin B, the resin B having a content of a fluorine atomper unit mass smaller than the content of a fluorine atom per unit massin the resin C.
 18. The method according to claim 17, wherein thesulfonic-acid-group-containing structural unit in one or both of theresin A and the resin B is represented by formula (1):

wherein in the formula (1), Ra is a hydrogen atom or a methyl group, andRb is a single bond or a divalent organic group.
 19. The methodaccording to claim 11, wherein the resin C does not contain asulfonic-acid-group-containing structural unit.
 20. The method accordingto claim 11, wherein the resin A further comprises acarboxyl-group-containing structural unit.
 21. The method according toclaim 11, wherein a receding contact angle of a film formed from theresin composition, with respect to water, is 80° or more.
 22. The methodaccording to claim 11, wherein the sulfonic-acid-group-containingstructural unit in the resin A is represented by formula (1):

wherein in the formula (1), Ra is a hydrogen atom or a methyl group, andRb is a single bond or a divalent organic group.